Production process of biomonomers and their precursors

Abstract

A process for producing biomonomers and their precursors. The furoate carboxylation reaction is carried out using particles formed from furoate and an alkali base, and optionally a reaction promoter. The particles may be in a slurry. The particles are exposed to gaseous carbon dioxide and heated. The reaction produces dicarboxylates, which can be isolated and used to produce biomonomers such as furandicarboxylate methyl ester and furandicarboxylic acid.

Description

[Technical Field]

[0001] (Statement of priority) This application claims priority to U.S. Provisional Patent Application No. 63 / 477,859, filed December 30, 2022, which is incorporated herein by reference in its entirety.

[0002] FIELD OF THE INVENTION The present invention relates generally to processes for producing aromatic carboxylic acid compounds, including furandicarboxylic acid and furandicarboxylic acid methyl ester, and their precursors from biomass. [Background technology]

[0003] Recently, processes have been developed for producing aromatic carboxylic acids and esters from sugars produced from biomass. These aromatic carboxylic acids and esters can be converted to dicarboxylates, which can then be utilized to produce monomers such as furan dicarboxylate methyl ester (FDME) and furan dicarboxylic acid (FDCA). As is known, these monomers are useful for making polymers and plastics and are sometimes referred to as biomonomers because they are derived at least in part from biomass.

[0004] These processes are desirable because they provide for the production of biomonomers, as opposed to producing chemicals and monomers from fossil fuel sources. Additionally, the processes are desirable because they can consume carbon dioxide, which is considered a greenhouse gas.

[0005] While biomonomers are generally effective for their intended purposes, there is a continuing desire and need to provide effective and efficient processes for producing biomonomers from biomass-derived components and carbon dioxide. Summary of the Invention

[0006] The present inventors have found that particle size and interparticle crystallization of the furoate, alkali base, and promoter components play an important role in controlling the activity of the reaction. In particular, smaller particle size and intergrown crystals result in significantly faster carboxylation reactions compared to reactions utilizing mixed powders. Therefore, forming small furoate feed particles prior to the carboxylation reactor facilitates the ability to provide a smaller reactor and / or achieve higher conversions.

[0007] Thus, in at least one aspect, the present invention can be characterized as providing a process for producing a biomonomer precursor by combining a furoate and an alkali base to form a mixture; forming particles from the mixture, the particles comprising the furoate and the alkali base; and heating the particles in the presence of carbon dioxide to form a dicarboxylate.

[0008] The particles may have an average particle size of 20 to 200 microns.

[0009] The particles may further comprise a carboxylate accelerant.

[0010] The particles may be spherical.

[0011] The particles may be formed in a hydrocarbon oil.

[0012] The particles may be formed by drying a portion of the effluent from the oxidation reaction zone. Drying may include spray drying and / or aqueous evaporation.

[0013] The mixture may be heated to a temperature of 150°C to 360°C at a pressure up to 6,895 kPa (1,000 psi).

[0014] The mixture may be a slurry and the carbon dioxide may be provided as bubbles flowing countercurrent to the slurry and particles.

[0015] The process may also include recovering the dicarboxylate and converting the dicarboxylate to dimethyl furandicarboxylate or furandicarboxylic acid, or both.

[0016] In another aspect, the invention may be broadly characterized as providing a process for producing furandicarboxylate methyl ester or furandicarboxylic acid from biomass-derived compounds by combining furoate and an alkali base to form a mixture; forming particles from the mixture, the particles comprising the furoate and the alkali base; heating the particles in the presence of carbon dioxide to form dicarboxylates; recovering the dicarboxylates; and converting the dicarboxylates to furandicarboxylate methyl ester or furandicarboxylic acid, or both.

[0017] The particles may further comprise a carboxylate accelerant.

[0018] The particles may be spherical.

[0019] The alkali base, the furoate counterion, or both, may be selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and mixtures thereof.

[0020] The furoate particles may have an average particle size of 20 to 200 microns.

[0021] The mixture is heated to a temperature between 150°C and 360°C at a pressure of up to 6,895 kPa (1,000 psi).

[0022] The mixture may be a slurry, which may be formed in a hydrocarbon having negligible solubility for the furoate salt and the alkali base.

[0023] Further aspects, embodiments and details of the invention, all of which may be combined in any manner, are set out in the detailed description of the invention below. [Brief explanation of the drawings]

[0024] One or more exemplary embodiments of the invention are described below in conjunction with the following drawing figures. [Figure 1] 1 is a photograph of a conventional powder mixture used in a carboxylation reaction. [Figure 2] 1 is a photograph of conventional co-evaporation materials used in carboxylation reactions. [Figure 3] 1 is a photograph of particles according to the present invention used in a carboxylation reaction. DETAILED DESCRIPTION OF THE INVENTION

[0025] As described above, the present invention provides a process utilizing the carboxylation reaction of furoate. Producing furoate from biomass is known. See U.S. Patent Nos. 7,572,925 and 8,772,515. As used herein, "biomass" includes, but is not limited to, lignin, plant parts, fruits, vegetables, plant processing waste, wood chips, rice husks, grains, grass, corn, corn husks, weeds, aquatic plants, hay, paper, paper products, recycled paper and paper products, and any combination thereof containing cellulose, lignin, or biological or biologically derived materials. Thus, while the process is intended to be used as part of an integrated facility for producing FDCA / FDME from C5 biomass, other implementations may be utilized.

[0026] Generally, this process involves mixing a furoate, such as a furoate salt, with an alkali base and, optionally, a carboxylate accelerant to form particles. These particles are heated to a reaction temperature in the presence of carbon dioxide gas. The furoate is converted to a dicarboxylate (FDCA salt), which can then be converted to either the FDCA free acid or FDME in subsequent chemical steps.

[0027] With these general principles in mind, one or more embodiments of the invention are described below with the understanding that the description is not intended to be limiting.

[0028] The method according to the present invention includes forming a mixture containing a furoate and an alkali base, and then drying the mixture to form particles. The mixture may further include a carboxylate accelerant, such as a hydrocarbon having an alpha C-H bond, such as acetate.

[0029] The alkali base may be a metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, and mixtures thereof.

[0030] Furoate counterions can include lithium, sodium, potassium, rubidium, cesium, and mixtures thereof.

[0031] The alkali base can be in a molar ratio of alkali base to furoate of 1:1 to 2:1, 1:0.1 to 1:1, 1:0.1 to 1:0.5, or 0.1:1 to 1:1.

[0032] It is contemplated that furoate is formed in an oxidation zone where biomass-derived components are subjected to a selective oxidation reaction process to produce furoate. The furoate can be separated from the other portion of the effluent mixed with the alkali base, as well as any reaction promoters, and then dried to form particles. Drying can include spray drying and / or aqueous evaporation. The particles may or may not be formed in a hydrocarbon oil.

[0033] Once formed, the particles preferably have an average particle size of from 20 to 200 microns, or from 40 to 100 microns, for example 60 microns. The particles are preferably spherical.

[0034] The components of the particles (furoate and alkali base) are uniformly distributed or distributed throughout the individual particles so that each particle is generally homogeneous in composition. This is in contrast to processes in which two different types of particles are formed simultaneously, with one type of particle contacting another type of particle. Thus, at least 10% by weight, or at least 20% by weight, or at least 30% by weight, or at least 40% by weight, or at least 50% by weight, or at least 60% by weight, or at least 70% by weight, or at least 80% by weight, or at least 90% by weight, or at least 95% by weight, or at least 99% by weight of the particles is formed by a mixture of at least the furoate and alkali base.

[0035] The particles can be fed into a hydrocarbon oil, e.g., a hydrocarbon material containing 5 to 30 carbon atoms per molecule and having paraffinic and / or aromatic functionality, to form a slurry. Generally, the hydrocarbon oil selected for the slurry has negligible solubility for the furoate and alkali base. It should be understood that the use of a slurry-phase reaction is merely preferred, and other reactors, such as solid-state reactors, may also be used. If the promoter is not included in the particles, it may be provided with the slurry or provided to the particles in another manner.

[0036] The formed particles are exposed to carbon dioxide gas and heated. When a slurry is used, the carbon dioxide can be bubbled into the slurry. The bubbles may flow countercurrently to the flow of the slurry, particularly the flow of the particles.

[0037] The particles, together with carbon dioxide, are heated at a pressure from atmospheric up to 6,895 kPa (1,000 psi), up to 4,826 kPa (700 psig), or up to 4,137 kPa (600 psig) at a temperature of 150-360°C, or 270-330°C, for a time sufficient to form a dicarboxylate via a carboxylation reaction between the carbon dioxide and the furoate. The reaction time is sufficient to produce an aromatic carboxylic acid compound, and may be from 1 second to 24 hours, 1 minute to 12 hours, 1 minute to 6 hours, or 1 minute to 1 hour. The process may be a continuous, semi-batch, or batch reaction process.

[0038] The dicarboxylates made can include terephthalic acid, naphthalic acid, thiophenedicarboxylic acid, pyridinedicarboxylic acid, carbazoledicarboxylic acid, and dibenzothiophenedicarboxylic acid. In particular, the dicarboxylate can be a furandicarboxylate, specifically furan-2,4-dicarboxylate and / or furan-2,5-dicarboxylate.

[0039] The dicarboxylates can be recovered, for example, by separation from the slurry. The recovered dicarboxylates can be converted to FDME, FDCA, or both. In particular, the biomonomers produced can include one or more of furan-2,5-dicarboxylic acid, furan-2,4-dicarboxylic acid, dimethylfuran-2,5-dicarboxylate, dimethylfuran-2,4-dicarboxylate, and salts thereof. These biomonomers can be converted to polymers as known in the art.

[0040] The separated slurry may be recycled or heat may be recovered from the separated slurry in a heat exchanger.

[0041] Particles formed from both furoate and alkali base provide an effective and efficient means for producing biomonomers and their precursors.

[0042] experiment Particles according to the invention (FIG. 3) were used in a carboxylation reaction and compared with a conventional powder mixture (FIG. 1) and co-evaporated material (FIG. 2). The feed for the carboxylation reaction was 1 molar equivalent of K-furoate, 0.55 molar equivalents of KCO, and 0.35 molar equivalents of K-acetate. The feed was heated to a temperature of 300°C for 5 hours in the presence of carbon dioxide. The conventional powder mixture (FIG. 1) was found to have a conversion of 69%, and the co-evaporated material was found to have a conversion of 79%. The particles according to the invention were found to have a conversion of 96%.

[0043] Specific Embodiments While the following will be described in conjunction with specific embodiments, it will be understood that this description is illustrative, but not intended to limit the scope of the preceding description and appended claims.

[0044] A first embodiment of the present invention is a process for producing a biomonomer precursor, the process comprising: combining furoate and an alkali base to form a mixture; forming particles from the mixture, the particles comprising furoate and the alkali base; and heating the particles in the presence of carbon dioxide to form dicarboxylates. An embodiment of the present invention is any one, any, or all of the preceding embodiments of this paragraph through the first embodiment of this paragraph, wherein the particles have an average particle size of 20 to 200 microns. An embodiment of the present invention is any one, any, or all of the preceding embodiments of this paragraph through the first embodiment of this paragraph, wherein the particles further comprise a carboxylate reaction accelerator. An embodiment of the present invention is any one, any, or all of the preceding embodiments of this paragraph through the first embodiment of this paragraph, wherein the particles are spherical. An embodiment of the present invention is any one, any, or all of the preceding embodiments of this paragraph through the first embodiment of this paragraph, wherein the particles are formed in a hydrocarbon oil. An embodiment of the invention is any one, any, or all of the preceding embodiments of this paragraph through the first embodiment of this paragraph, wherein the particles are formed by drying a portion of the effluent from the oxidation reaction zone. An embodiment of the invention is any one, any, or all of the preceding embodiments of this paragraph through the first embodiment of this paragraph, wherein the drying comprises spray drying. An embodiment of the invention is any one, any, or all of the preceding embodiments of this paragraph through the first embodiment of this paragraph, wherein the drying comprises aqueous evaporation. An embodiment of the invention is any one, any, or all of the preceding embodiments of this paragraph through the first embodiment of this paragraph, wherein the mixture is heated to a temperature of 150°C to 360°C at a pressure of up to 6,895 kPa (1,000 psi). An embodiment of the invention is any one, any, or all of the preceding embodiments of this paragraph through the first embodiment of this paragraph, wherein the mixture comprises a slurry. An embodiment of the invention is any one, any, or all of the preceding embodiments of this paragraph through the first embodiment of this paragraph, wherein carbon dioxide is provided as gas bubbles countercurrent to the slurry and particles.An embodiment of the present invention is one, any, or all of the preceding embodiments in this paragraph through the first embodiment of this paragraph, further comprising recovering the dicarboxylate and converting the dicarboxylate to dimethyl furandicarboxylate or furandicarboxylic acid, or both.

[0045] A second embodiment of the present invention is a process for producing furandicarboxylate methyl ester or furandicarboxylic acid from biomass-derived compounds, the process comprising: combining furoate and an alkali base to form a mixture; forming particles from the mixture, the particles comprising furoate and the alkali base; heating the particles in the presence of carbon dioxide to form dicarboxylates; recovering the dicarboxylates; and converting the dicarboxylates to furandicarboxylate methyl ester or furandicarboxylic acid, or both. An embodiment of the present invention is one, any, or all of the preceding embodiments in this paragraph through the second embodiment of this paragraph, wherein the particles further comprise a carboxylate reaction accelerator. An embodiment of the present invention is one, any, or all of the preceding embodiments in this paragraph through the second embodiment of this paragraph, wherein the particles are spherical. An embodiment of the present invention is one, any, or all of the preceding embodiments in this paragraph through the second embodiment of this paragraph, wherein the alkali base, furoate counterion, or both, is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and mixtures thereof. An embodiment of the invention is one, any, or all of the preceding embodiments of this paragraph up to the second embodiment of this paragraph, wherein the furoate particles have an average particle size of 20 to 200 microns. An embodiment of the invention is one, any, or all of the preceding embodiments of this paragraph up to the second embodiment of this paragraph, wherein the mixture is heated to a temperature of 150°C to 360°C at a pressure of up to 6,895 kPa (1,000 psi). An embodiment of the invention is one, any, or all of the preceding embodiments of this paragraph up to the second embodiment of this paragraph, wherein the mixture comprises a slurry. An embodiment of the invention is one, any, or all of the preceding embodiments of this paragraph up to the second embodiment of this paragraph, wherein the slurry is formed in a hydrocarbon having negligible solubility for the furoate salt and the alkali base.

[0046] Without further elaboration, it is believed that, using the preceding description, one skilled in the art can utilize the present invention to its fullest extent and easily ascertain the essential characteristics of the present invention, and can make various changes and modifications to the present invention to adapt it to various uses and conditions, without departing from the spirit and scope of the present invention. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way, and are intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

[0047] Above, all temperatures are set forth in degrees Celsius and all parts and percentages are by weight unless otherwise indicated.

[0048] While at least one exemplary embodiment has been presented in the foregoing detailed description of the present invention, it should be understood that numerous variations exist. It should also be understood that the exemplary embodiment(s) are merely examples, and are in no way intended to limit the scope, applicability, or configuration of the present invention. Rather, the foregoing detailed description provides those skilled in the art with a convenient guide for implementing exemplary embodiments of the present invention, and it should be understood that various changes can be made in the functions and arrangement of elements described in the exemplary embodiment without departing from the scope of the present invention as set forth in the appended claims and their legal equivalents.

Claims

1. 1. A process for producing a biomonomer precursor, said process comprising: combining a furoate and an alkali base to form a mixture; forming particles from the mixture, the particles comprising the furoate and the alkali base; and heating the particles in the presence of carbon dioxide to form a dicarboxylate.

2. The process of claim 1, wherein the particles have an average particle size of 20 to 200 microns.

3. The process of claim 1 , wherein the particles further comprise a carboxylate accelerant.

4. The process of claim 1 , wherein the particles are spherical.

5. The process of any one of claims 1 to 4, wherein the particles are formed in a hydrocarbon oil.

6. The process of any one of claims 1 to 4, wherein the particles are formed by drying a portion of the effluent from an oxidation reaction zone.

7. 7. The process of claim 6, wherein the drying comprises spray drying.

8. The process of claim 6 , wherein the drying comprises aqueous evaporation.

9. 5. The process of any one of claims 1 to 4, wherein the mixture is heated to a temperature of from 150°C to 360°C at a pressure of up to 6,895 kPa (1,000 psi).

10. The process of any one of claims 1 to 4, wherein the mixture comprises a slurry.

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